Oxygen-clustering in graphene oxide is the activated process of diffusion of oxygen functionalities: hydroxyls and epoxides, to form clusters and to trigger sp2 percolation, a key element for electrical conductivity. Impact of oxygen-clustering is thoroughly analyzed in electrochemically-derived graphite oxide (EGO), amine-functionalized frameworks (EGOF), and their pyrolyzed forms. Amine pillars within EGOF were suspected to amplify oxygen-clustering in EGOF as onset temperature of thermal decomposition was smaller in EGOF than in EGO. Thermochemical analysis proves that pillars within EGOF significantly augment oxygen-clustering aiding the reduction mechanism as inferred by the activation energy of thermal decomposition. Defective oxygen-clustering mechanism is evidenced using multiple techniques, including XRD, and is harnessed to enhance nitrogen doping. The pyrolytic morphological transformation from lamellae of EGOF into ravioli is revealed through SEM. A labyrinthic network of array prismatic dislocations provides stability to pyrolyzed EGOF ravioli whilst confining long chains of electron delocalization (localized π-orbitals), as unprecedently confirmed by HR-TEM/EELS and conductive AFM (C-AFM). Oxygen-clustering not only improves nitrogen doping in ravioli, but also improves density of array prismatic dislocations, which ultimately boosts Faradaic redox activity as observed in cyclic voltammetry (CV). Results show that Faradaic response originating from redox-active nitrogen groups predominantly relies on abundance of extended localized π-orbitals, which are geometrically and chemically confined within ravioli array prismatic dislocations. Our first-of-a-kind HR-TEM/EELS, C-AFM, and CV comparative and correlative analysis of pyrolyzed forms of EGO, EGOF, and their oxygen-clustered derivatives, confirms emergent role of confined electron delocalizations in amplifying Faradaic redox activity.